Sulfuric Acid and Oleum

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CHEMICAL ENGINEERING CALCULATIONS 2

(ChE11 – A2)

PROFESSOR: EDWIN RICHARD R. ORTIZ, M. Eng

TITLE: Stoichiometry of fuel combustion: Production of Sulfuric Acid and Oleum

SUBMITTED AND REPORTED BY:


Achas, Carah
Centural, Bernadeth Jan
Valmoria, Arvin
PRODUCTION OF
SULFURIC ACID AND OLEUM
OLEUM
 A dense corrosive liquid consisting of concentrated
sulfuric acid and excess sulfur trioxide in solution.
 EMPIRICAL FORMULA: H2S2O7
Methods of producing sulfuric acid and oleum

 Contact Process
- Can produce concentrated H2SO4 and oleum

 Chamber Process
- Produces weak H2SO4
- Cannot produce oleum
CONTACT PROCESS
Raw sulfur, 96% is burned in dry excess air producing a gas with an orsat analysis of
18%SO2, 0.50%O2, and 81.50%N2. The burner gases are fed to a catalytic
converter together with 20% excess secondary air resulting n the oxidation of 60% of
the SO2 to SO3. the gases from the converter enter an absorber to produce the acid.
Assuming no further oxidation of the SO2 taking place in the absorber, calculate:
a) Complete analysis of the burner gas
b) Complete analysis of the converter gas
c) Wt. of an 85% concentrated H2SO4 solution per kg raw S charged if the absorbing
acid is 40%H2SO4
d) Wt. of a 5% oleum formed per kg raw S charged if the absorbing acid is a
90%H2SO4 solution.
SOLUTION: Basis 100 moles SO3 free burner gas
Burner Analysis:
Primary O2 from air = 81.5(21/79) = 21.66 moles O2
O2 unaccounted = 21.66 – 18 – 0.5 = 3.16 mole O2
S converted to SO3 = 3.16(2/3) = 2.10 moles SO3 formed in BG
Total wt. of raw S = (2.10 + 18.0)(32)(1/0.96) = 670

a) Complete analysis of Burner Gas (ANS)


GAS n n%
SO2 18 17.63%
O2 0.5 0.49%
N2 81.5 79.82%
SO3 2.1 2.06%
Total 102.1
Converter Analysis:
Theo O2 for complete conversion of SO2 to
SO3
=(1/2)(nSO2) – (moles free O2 in burner gas)
=(1/2)(18) – (0.5) = 8.5

Secondary O2 from air = (8.5)(1.2) = 10.2


Secondary N2 from air = (10.2)(79/21) = 38.37

SO2 converted to SO3 = (0.6)(18) = 10.8 b) Complete analysis of Converter Gas


reaction: SO2 + ½ O2  SO3 (ANS)
(10.8) (5.4) (10.8)
GAS n n%
SO2 7.2 4.96
SO2 unreacted = 18 – 10.8 = 7.2 O2 5.3 3.65
O2 after reaction = 0.5 + 10.2 – 5.4 = 5.3 N2 119.87 82.51
N2 after reaction = 81.5 + 38.37 = 119.87 SO3 12.9 8.88
SO3 after reaction = 2.1 + 10.8 = 12.9 TOTAL 145.27
Absorber Analysis:
Let y = wt of 85% H2SO4 solution formed
y – 12.9(80) = y – 1032 = wt. of 40% H2SO4 used
H2SO4 balance:
0.4(y – 1032) + 1032(98/80) = 0.85y
y = 1892kg/100 moles SO3 free burner gas
c) Wt. of 85% acid/kg raw S = 1892/670 = 2.823 (ANS)
Let z = wt. of 5% oleum formed
z – 1032 = wt. of 90% H2SO4 acid used
SO3 balance:
0.9(z – 1032) (80/98) + 1032 = 0.05z + 0.95z(80/98)
z = 3014.83kg/100 moles SO3 free burner gas
d) Wt. of 5% oleum/kg raw S = 3014.83/670 = 4.5 (ANS)

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